In general, for the purpose to obtain a color image by processing a silver halide color photographic light-sensitive material having been exposed to light, it is necessary to treat the developed metallic silver with an agent having a bleaching ability after the color-developing process.
As the solution having bleaching ability, bleaching solution and bleach-fixing solution are known. The bleaching solution is used by combining with a succeeding fixing process in which the developed silver halide is fixed. The bleach-fixing solution is used for the purpose to carry out both the bleaching and fixing process in one stage.
In the treating procedure of silver halide color photographic light-sensitive materials the bleaching is carried out by using a solution containing an inorganic oxidizing agent such as potassium iron (III) cyanate (red prussiate) or a dichromate as the oxidizing agent to bleach the developed silver.
Such bleaching solutions containing an inorganic oxidizing agent have several serious weakpoints. Potassium iron (III) cyanate or a dichromate has a comparatively good bleaching ability for the developed silver but either of them is possibly produce cyanate ion or hexavalent chromium ion by photochemical decomposition and both of which are not preferable for environmental protection since they are harmful to human health. Moreover, oxidizing power of these oxidizing agents is too strong to let them coexist with a fixing agent (an agent to solubilize the developed silver halide such as a thiosulfate). Since then, it is almost impossible to apply these oxidizing agents for a bleach-fixing agent and is also difficult to simplify and shorten the treatment. And what is worse, the used solutions containing these oxidizing agents are difficult to reuse by reclamation and recirculation.
For the purpose to improve these short points and environmental hazards metal complex salts of organic acids such as an aminopolycarbonate metal complex have come to be used as oxidizing agents which are possible to simplify and shorten the process and, moreover, the reuse of waste solution is also possible. However, the bleaching speed of the developed silver (metallic silver) which is formed by the developing process is slow since the oxidizing power of these organic complexes is weak. For example, iron (III) ethylenediaminetetraacetate complex (it is assumed to have a strong bleaching power among metallic complexes of aminocarboxylic acids) is practically utilized as a bleaching solution or a bleaching-fixing solution. However, when they are applied for highly sensitive silver halide color photographic light-sensitive materials mainly composed from silver bromide or silver iodobromide emulsions, especially for a negative or a reversal color-photographic films containing silver iodide, their bleaching power and silver-removing power are not sufficient resulting the remaining of a trace amount of image silver after the prolonged treatment. This tendency is remarkable in case of bleach-fixing solutions in which an oxidizing agent, thiosulfate and sulfite are coexisting since the oxidation-reduction potential of the solution is lowered. Especially, the removal of silver is remarkably deficient in case of highly sensitive silver iodide-containing silver halide color photographic light-sensitive materials containing black colloidal silver for antihalation.
This phenomenon is more remarkably observed in case of newly-developed "core-shell emulsion" which is a kind of a silver iodide containing highly sensitive emulsion having fine grain and is very preferable for the porpose of resources conservation since silver is effectively used. This core-shell emulsion is a monodispersed emulsion which is made by using a precedent silver halide emulsion as the crystalline core on which the subsequently-developed precipitate is piled successively one after another--that is, prepared by intentionally controlling the composition or the environment of the precipitation. Above all, a core-shell type highly sensitive emulsion containing silver iodide in core and/or the shell has a very preferable photographic characteristics. But when it is applied for silver halide color photographic light-sensitive materials the bleaching and fixing abilities for developed silver and silver halide are very inferior.
That is to say, in the case of the developed silver of photographic silver halide emulsions which belongs to a core-shell emulsion containing not less than 0.5 mol% of silver halide both in the core and the shell, the sensitivity, granularity and covering power are superior but the bleaching power is remarkably inferior since the developed silver of color photographic light-sensitive materials is necessary to be bleached and its configuration is different from the conventional ones. Photographic sensitive materials using emulsions containing tabular type silver halide grains (for example, described in Japanese Patent Publication Open to Public Inspection Nos. 113930/1983, 113934/1983, 127921/1983 and 108532/1983) do not increase the spent amount of silver and do not worsen its picture quality due to its tabular nature even when the number of light quantum caught by silver halide grain increases. However, even in the case of these tubular type grains there is one short point that the bleaching quality of silver formed by development using a p-phenylene-diamine type color-developing agent.
The inventors found that even in the case of the highly sensitive fine-grain silver halide color photographic light-sensitive materials containing black colloidal silver as the anti-halation layer and, at least, three layers of silver halide emulsions all of which contain at least 0.5 mol% silver iodide the bleach-fixing agent containing an iron (III)-complex of organic acid can sufficiently desilver when the total amount of coated silver, the total thickness of photographic coated materials and the swelling velocity of binder (T 1/2) are lower than the specific values, respectively.
There happened, however, another problem that the cyan dye loss is worsen due to the shortening of bleaching-fixing time. Since then, the developing of a treating procedure of silver-halide color photographic light-sensitive materials is demanded by which the above-mentioned silver halide color photographic light-sensitive materials can be bleached and fixed quickly and the cyan dye loss is not worsen.